1. Field of the Invention
The present invention relates to new substituted 2,5-diamino-1-aminomethylbenzene compounds and oxidation dye precursor compositions for dyeing keratin fibers, especially human hair, containing these compounds.
2. Prior Art
Oxidation dyes have been important in the field of dyeing keratin fibers, especially human hair, for a long time. Dyeing occurs by reaction of certain developer substances alone or with certain coupler substances in the presence of a suitable oxidizing agent. It is known from DE-PS 47349 that keratin fibers can be dyed in bright blond to bluish-black color tones by p-phenylenediamine according to the oxidizing agent used. Blue color tones are produced however by a combination of p-phenylenediamine and its derivative compounds with certain coupler substances. Since only compounds that have specifications or properties that, on the one hand, protect the user sufficiently and, on the other hand, produce a stable resistant color that lasts for a sufficient time can be employed, the selection of suitable developer and coupler substances is limited.
It has now been surprisingly found that certain p-phenylenediamine derivative compounds permit dyeing of keratin fibers, especially human hair, an intense blue color, even without addition of a coupler substance.
Thus intense colors, which are extraordinarily light-fast and wash-fast, are obtained when these p-phenylenediamine derivative compounds are used in an oxidizing medium
According to the present invention these p-phenylenediamine derivative compounds are substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I), or their physiologically compatible water-soluble salts, 
wherein
R1, R2, R3, R4, R5, R6 and R7, independently of each other, each represent H, a C1- to C6-alkyl group, a C1- to C4-hydroxyalkyl group, a C2- to C4-dihydroxyalkyl group or a C1- to C4-alkoxy-(C1- to C2-)alkyl group or R1 and R2 and/or R3 and R4 and/or R5 and R6 together with the N atom form a four-member to eight-member aliphatic ring, with the proviso that at least two of the groups R1 to R6 each represent hydrogen;
R8 represents hydrogen, a halogen atom, a C1- to C4-alkyl group, a C1- to C4-hydroxyalkyl group or a C1- to C4-alkoxy group;
R9 represents a hydrogen, a halogen atom, a cyano group, a hydroxy group, a C1- to C4-alkoxy group, a C1- to C4-hydroxyalkoxy group, a C1- to C6-alkyl group, a C1- to C4-alkylthioether group; a mercapto group; an amino group, a C1- to C4-alkylamino group, a C1- to C4-hydroxyalkylamino group, a di(C1- to C4-alkyl)amino group, a di(C1- to C4-hydroxyalkyl)amino group, a {dihydroxy(C2- to C4)-alkyl}amino group, a (C1- to C4-hydroxyalkyl)-C1-C4-alkylamino group, a trifluoromethane group, a C1-C4-hydroxyalkyl group or a C3-C4 dihydroxyalkyl group; and
R10 represents hydrogen or a C1- to C6-alkyl group.
For example, the following compounds of formula (I) can be named as examples: 2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-bis(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((3-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene; 2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-bis-(hydroxyethyl)aminophenylamino)methyl)-1,4-diaminobenzene; 2-((4-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((2-aminophenylamino)methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((2-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N1, N1-bis-(hydroxyethyl)-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((3-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((3-bis-(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((2-aminophenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((3-bis(hydroxyethyl)amino-phenylamino)methyl)1,4-diaminobenzene; N1-hydroxyethyl-2-((3-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((4-bis(hydroxyethyl)-aminophenylamino)-methyl)-1,4-diaminobenzene; N1-hydroxyethyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis-(hydroxyethyl)-2-((2-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((2-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((3-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((3-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis-(hydroxyethyl)-2-((4-bis(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((2-aminophenylamino)-methyl)-1,4-diaminobenzene, N4-dihydroxypropyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((2-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((3-bis-(hydroxyethyl)aminophenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((3-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-dimethylaminophenylamino)-methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((2-aminophenylamino)methyl)-1,4-diaminobenzene, N4-hydroxyethyl-2-((2-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((2-dimethylamino-phenylamino)-methy)-1,4-diaminobenzene; N4-hydroxyethyl-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene-N4-hydroxyethyl-2-((3-bis(hydroxy-ethyl)amino-phenylamino)methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((3-dimethylaminophenylamino)methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((4-aminophenylamino)-methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((4-bis(hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-hydroxyethyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(dihydroxypropyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-hydroxyethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((methyl-(2-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(2-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(2-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(3-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(3-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(3-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(4-(dihydroxypropylamino)-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(4-amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(4-bis(hydroxyethyl)amino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((1-(2-amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(2-bis(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(2-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(3-aminophenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(3-bis(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(3-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(4-amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(4-bis-(hydroxyethyl)amino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((1-(4-dimethylamino-phenyl)-amino)-ethyl)-1,4-diaminobenzene; 2-((2-((2,3-diamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-((2,4-diamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-((3,4-diamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((methyl-(2,3-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(2,4-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-((methyl-(3,4-diamino-phenyl)-amino)-methyl)-1,4-diaminobenzene; 2-(1-(2,3-diamino-phenylamino)-ethyl)-1,4-diaminobenzene; 2-(1-(2,4-diamino-phenylamino)-ethyl)-1,4-diaminobenzene; 2-(1-(3,4-diamino-phenylamino)-ethyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethoxy)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-hydroxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethoxy)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-hydroxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-chloro-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-hydroxy-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-methyl-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-(3-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((5-methyl-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-(2-hydroxyethoxy)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-(2-hydroxyethyl)-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-chloro-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-hydroxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((6-methoxy-2-amino-phenylamino)-methyl)-1,4-diaminobenzene 2-((6-methyl -2-amino-phenylamino)-methyl)-1,4-diaminobenzene.
Compounds of formula (I) are preferred, in which (i) R1, R2, R2 and R4 are each hydrogen and/or (ii) one or more of the groups R5 to R10 are each hydrogen and/or (iii) R5 and R6, independently of each other, are hydrogen, a methyl group or a C1- to C4-hydroxyalkyl group or (iv) R7, R8, R9 and R10 are each hydrogen and R5 and R6 are, independently of each other, hydrogen, a C1- to C4-alkyl group, a C1- to C4-hydroxyalkyl group or a C2- to C4-dihydroxyalkyl group or R5 and R6 together with the N atom form a four-member ring.
The following compounds of formula (I) are particularly preferred: 2-((2-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene; 2-((4-amino-phenylamino)methyl)-1,4-diaminobenzene; 2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-dimethylamino-phenylamino)methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((3-aminophenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1,N1-bis(hydroxyethyl)-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)methyl)-1,4-diaminobenzene; N1-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((3-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxy-ethyl)-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4,N4-bis(hydroxyethyl)-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; N4-dihydroxypropyl-2-((4-dimethylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(pyrrolidin-1-yl)-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-dihydroxypropylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-methylamino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methyl-4-aminophenylamino)-methyl)-1,4-diaminobenzene; 2-((2-methyl-4-bis(2-hydroxy-ethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethyl)-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-(2-hydroxyethyl)-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-chloro-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-chloro-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methoxy-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methoxy-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methyl-4-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((3-methyl-4-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethoxy)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethoxy)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene; 2-((4-(2-hydroxyethyl)-3-amino-phenylamino)-methyl)-1,4-diaminobenzene and 2-((4-(2-hydroxyethyl)-3-bis(2-hydroxyethyl)amino-phenylamino)-methyl)-1,4-diaminobenzene.
The compounds of formula (I) can be used both as free bases and also in the form of their physiologically compatible salts with inorganic or organic acids, for example with hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.
The manufacture of the substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I) can take place using known synthetic methods. The synthesis of the compounds of the invention, for example, can be performed as follows: either a) by reductive amination of a substituted benzene compound of formula (II): 
with an amine of formula (III) and subsequent splitting off of the protective group; 
wherein the R groups in formula (II) and (III) have the following significance:
Ra represents a protective group, such as described, for example, in the chapter xe2x80x9cProtective Groups in Organic Synthesisxe2x80x9d, Chapter 7, Wiley Interscience, 1991;
Rb represents NR1Ra or NR1R2, while
X, R1, R2, R5, R6, R7, R9 and R10 have the same significance as in formula (I); or
b) by substitution of a substituted benzene compound of formula (IV) 
xe2x80x83with an amine of formula HNR1R2, reduction of the nitrile group, alkylation of the amino group with a compound of formula (V) and subsequent reduction of the nitrile group; 
xe2x80x83wherein in formula (IV) and (V) X represents a halogen atom and R1, R2, R5, R6 and R9 have the same significance as in formula (I).
The substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I) are soluble in water and provide colors with higher color intensity or depth and outstanding color fastness, especially light fastness, wash fastness and rubbing fastness.
The subject matter of the present invention also includes oxidation dye precursor compositions for oxidative dyeing of keratin fibers, which necessarily contain at least one of the substituted 2,5-diamino-1-aminomethylbenzene compounds of formula 1.
These oxidation dye precursor compositions according to the invention contain about 0.005 to 20, preferably from 0.01 to 10, percent by weight of the substituted 2,5-diamino-1-aminomethylbenzene compound of formula I. A content of from 0.10 to 8 percent by weight of the substituted 2,5-diamino-1-aminomethylbenzene compound of formula (I) is especially preferred.
The compounds of formula (I) dye keratinic material in intense blue color shades when other dyestuffs are not present. To obtain other color shades additional oxidation dyestuffs, for example developer substances or coupler substances, can be used alone or in mixture with each other, together with at least one compound of formula (I).
Preferred coupler compounds for use with the compounds of formula (I) in the compositions according to the invention include 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene, 5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline, 3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane, di(2,4-diaminophenoxy)-methane, 1,3-diamino-2,4-dimethoxybenzene, 2,6-bis-(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-aminophenol, 2-[(3-hydroxyphenyl)amino]acetamide, 5-[(2-hydroxyethyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethylphenol, 2-(4-amino-2-hydroxy-phenoxy)ethanol, 5-[(3-hydroxy-propyl)amino]-2-methylphenol, 3-[(2,3-dihydroxypropyl)amino]-2-methylphenol, 3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine, 5-amino-4-chloro-2-methylphenol, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate, 1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 1,2-dichloro-3,5-dihydroxy-4-methylbenzene, 1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methyl-benzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and 2,3-indolindione.
Preferred developer compounds for use with the compounds of formula (I) in the compositions of the invention include 1,4-diaminobenzene; 1,4-diamino-2-methylbenzene; 1,4-diamino-2,6-dimethylbenzene; 2,5-diamino-1,3-diethylbenzene dihydrochloride; 1,4-diamino-2,5-dimethylbenzene; 1,4-diamino-2,3-dimethylbenzene; 2-chloro-1,4-diamino-benzene; 1,4-diamino-2-(thiophen-2-yl)benzene dihydrochloride; 1,4-diamino-2-(thiophen-3-yl)benzene dihydrochloride; 3-(2,5-diaminophenyl)pyridine trihydrochloride; 2,5-diamino-biphenyl dihydrochloride; 1,4-diamino-2-(methoxy-methyl)benzene dihydrochloride; 1-(aminomethyl)-2,5-diaminobenzene-dihydrochloride; 1,4-diamino-2-(hydroxymethyl)benzene; 1,4-diamino-2-(2-hydroxyethoxy)-benzene dihydrochloride; 2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene dihydrochloride; 4-phenylaminoaniline; 4-dimethylaminoaniline; 4-(dipropylamino)aniline; 4-diethylaminoaniline; 4-(ethyl(2-hydroxyethyl)amino)-aniline; 4-(di(2-hydroxyethyl)amino)-aniline; 4-(di(2-hydroxyethyl)amino)-2-methylaniline; 4-((2-methoxyethyl)amino)-aniline; 4-((3-hydroxypropyl)amino)-aniline; 4-((2,3-dihydroxypropyl)amino)aniline; 1,4-diamino-2-(2-hydroxyethyl)-benzene; 1,4-diamino-2-(1-methylethyl)benzene; 1,3-bis-((4-aminophenyl)-(2-hydroxyethyl)amino)-2-propanol; 1,4-di((4-aminophenyl)amino)butane; 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane; 4-aminophenol; 4-amino-3-methylphenol; 4-amino-3-(hydroxymethyl)phenol; 4-amino-3-fluorophenol; 4-methylaminophenol; 4-amino-2-(aminomethyl)-phenol; 4-amino-2-(hydroxymethyl)phenol; 4-amino-2-fluorophenol; 4-amino-2-((2-hydroxyethyl)amino)-methylphenol; 4-amino-2-methylphenol; 4-amino-2-(methoxymethyl)phenol; 4-amino-2-(2-hydroxyethyl)-phenol; 5-aminosalicylic acid; 2,5-diaminopyridine; 2,4,5,6-tetraaminopyrimidine; 2,5,6-triamino-4(1H)-pyrimidone; 4,5-diaminobenzene; 1-(2-hydroxyethyl)-1H-pyrazole; 4,5-diamino-1-(1-methylethyl)-1H-pyrazole; 4,5-diamino-1-((4-methylphenyl)methyl)-1H-pyrazole; 1-((4-chlorophenyl)methyl)-4,5-diamino-1H-pyrazole and 4,5-diamino-1-methyl-1H-pyrazole.
The oxidation dye precursor compositions according to the invention can also contain additional dye compounds, for example 2-aminophenol, 2-amino-6-methylphenol and 2-amino-5-methylphenol, as well as other direct-dyeing dye compounds, such as triphenylmethane dye compounds, for example 4-[(4xe2x80x2-aminophenyl)-(4xe2x80x2-imino-2xe2x80x3,5xe2x80x3-cyclohexadien-1xe2x80x3-yliden)-methyl]-2-methyl-aminobenzene monohydrochloride (C.I. 42 510) and 4-[(4xe2x80x2-amino-3xe2x80x2-methyl-phenyl)-(4xe2x80x3-imino-3xe2x80x3-methyl-2xe2x80x3,5xe2x80x3-cyclohexadien-1xe2x80x3-yliden)-methyl]-2-methyl-aminobenzene monohydrochloride (C.I. 42 520); aromatic nitro dye compounds, such as 4-(2xe2x80x2-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol, 2-amino-5-(2xe2x80x2-hydroxyethyl)amino-nitrobenzene, 2-chloro-6-(ethyl-amino)-4-nitrophenol, 4-chloro-N-(2-hydroxyethyl)-2-nitroaniline, 5-chloro-2-hydroxy-4-nitroaniline, 2-amino-4-chloro-6-nitrophenol and 1-[(2xe2x80x2-ureidoethyl)-amino-4-nitrobenzene; azo dye compounds, for example 6-[(4xe2x80x2-aminophenyl)-azo]-5-hydroxy-naphthalene-1-sulfonic acid sodium salt (C.I. 14 805) and dispersion dye compounds, such as 1,4-diaminoanthraquinone and 1,4,5,8-tetra-aminoanthraquinone. The compositions according to the invention can contain these additional dye compounds in amounts of about 0.1 to 4.0 percent by weight. For example, it is possible to obtain blond to brown hair colors using a combination of the compounds of formula (I) with 2-aminophenol, 2-amino-6-methylphenol or 2-amino-5-methylphenol.
Understandably the coupler compounds and developer compounds as well as the other dye compounds, in so far as they are bases, may be used in the form of their physiologically compatible salts with organic or inorganic acids, such as hydrochloric or sulfuric acid. In so far as they have aromatic OH groups they may be used in the form of salts with bases, for example as alkali metal phenolates.
Furthermore in the case of oxidation hair dye precursor compositions, used for dyeing hair, still other conventional cosmetic additives may be included in the compositions. These conventional cosmetic additive ingredients include, for example, antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, complex formers, wetting agents, emulsifiers, thickeners and care materials. The form of these preparations containing the dyeing agents according to the invention can, for example, be a solution, especially an aqueous or aqueous-alcoholic solution. However the forms of the preparation according to the invention that are particularly preferred include a cream, a gel and an emulsion. These preparations comprise a mixture of the dye compounds according to the invention together with the conventional cosmetic additive suitable for these preparations.
Conventional additive ingredients for the solutions, creams, emulsions or gels include, for example, solvents, such as water, lower aliphatic alcohols, such as ethanol, propanol or isopropanol, glycerol or glycols, such as 1,2-propylene glycol; wetting agents or emulsifiers from the classes of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants, such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyltrimethyl ammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanol amides and ethoxylated fatty acid esters; thickeners, such as higher fatty alcohols, starches, cellulose derivatives, petrolatum, paraffin oils and fatty acids; as well as care materials, such as cationic resins, lanolin derivative compounds, cholesterol, pantothenic acid and betaine. The above-mentioned additive ingredients are used in amounts suitable for their purposes, for example the wetting agents and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25% by weight and the care materials in a concentration of about 0.1 to 5.0 percent by weight.
The oxidation dye precursor compositions according to the invention can react weakly acidic, neutral or alkaline according to their composition. They can especially have a pH of 6.0 to 11.5, preferably adjusted with ammonia. The pH however can be adjusted with organic amines, for example monoethanolamine and triethanolamine, or inorganic bases, such as sodium hydroxide and potassium hydroxide. Inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid, can be used for adjustment of pH in the acid range.
In order to use the oxidation dye precursor composition according to the invention for dyeing hair immediately prior to application to the hair a sufficient amount of this dye precursor composition for dyeing the hair, generally about 60 to 200 g, is mixed with an oxidizing agent. Then the resulting ready-to-apply dye mixture is applied to the hair.
Primarily hydrogen peroxide, or its addition compound with urea, melamine, sodium borate or sodium carbonate, is used as oxidizing agent to develop the hair colors, in the form of a 3- to 12-percent, preferably 6-percent, aqueous solution, however air oxygen can also be considered. If a 6-percent hydrogen peroxide solution is used as oxidizing agent, the weight ratio of oxidation dye precursor composition and oxidizing agent is 5:1 to 1:2, preferably however 1:1. Larger amounts of oxidizing agent are above all used with higher dye compound concentrations in the oxidation dye precursor composition, or if a a more intense bleaching or lightening of the hair color is intended at the same time. The ready-to-apply dye mixture is allowed to act on the hair for about 10 to 45 minutes, preferably 30 minutes, at 15 to 50xc2x0 C., after being applied to the hair. Then the dye mixture is rinsed from the hair with water and the hair is dried. If necessary the hair may be washed with a shampoo in connection with the rinsing and after-rinsed with a weak organic acid, for example citric or tartaric acid, as needed. Finally the hair is dried.
The oxidation dye precursor compositions containing the substituted 2,5-diamino-1-aminomethylbenzene compounds of formula (I) provide dyed hair colors having outstanding color fastness, especially light fastness, wash fastness, and fastness to rubbing. They provide a broad palette of various color shades and tones, which extend from blond shades to brown, purple, violet up to blue and black color shades according to the type and amounts of their various dye compound ingredients. The very good dyeing properties of the dye precursor compositions according to the invention are characterized by the fact that they can dye gray, chemically undamaged hair without difficulties and with good color coverage or color depth. The compounds of formula I also can be employed to produce intense blue colors on keratin fibers without addition of other dye compounds.
The following examples should illustrate the subject matter of the present invention in detail, without limiting the broad concept of the invention or the claims appended hereinbelow.